Methods and apparatus for controlled chemical vapor deposition

ABSTRACT

A gas injector system is provided that allows for improved distribution and directional control of the vapor material in a CVD or CVI process. Gas injector systems may be used without experiencing significant clogging of gas injector tube apertures over multiple. CVD procedures. Further, a gas injector system provided includes a dual aperture release system and/or allow vapor material to flow both substantially horizontally and substantially vertically.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority to and is a divisionalapplication of U.S. patent application Ser. No. 12/395,414, filed Feb.27, 2009 and entitled, “METHODS AND APPARATUS FOR CONTROLLED CHEMICALVAPOR DEPOSITION.” The '414 Application is incorporated by reference inits entirety.

FIELD OF INVENTION

The present invention relates to chemical vapor infiltration (CVI) andchemical vapor deposition (CVD), more particularly, apparatus andmethods for gas injectors used in conjunction with CVD/CVI and gasinjector systems that have extended useful lives.

BACKGROUND OF THE INVENTION

Chemical vapor infiltration (CVI) and chemical vapor deposition (CVD)are well-known processes for forming composite materials. CVI/CVD areparticularly useful processes for fabricating structural composites suchas brake disks, combustors and turbine components, and CVD/CVI are alsoused to fabricate various semiconductor products and other electronicparts. In general, the term CVI implies deposition of a matrix withinthe pores of a substrate, and the term CVD implies deposition of asurface coating on a substrate. However, as used herein, both terms areintended to refer generally to infiltration and/or deposition of amaterial on or within a substrate.

In general, CVD is a process of subjecting a substrate to a material invapor form, resulting in a deposition of the material on the substrate.CVD may be performed at various temperatures and pressures, and forvarious periods of time. In many applications, CVD is performed at hightemperatures and under low pressures, including under a vacuum or nearvacuum. To facilitate high temperatures, CVD may be performed in afurnace or other suitable vessel. In many applications, CVD is performedon multiple substrates concurrently for economic and efficiency reasons.To facilitate uniform application of vapor material onto a substrate,the flow rate, direction, duration, and dispersion of the vapor materialmay be controlled.

CVD may be used to deposit material onto substrates of various shapesand configurations, including annular disks, in such applications, thevapor material (i.e., chemicals in gaseous form) may be released intothe vessel via a central tube that is disposed perpendicular to thesurface of the annular disks. Vapor material is released into a vesselusing various methods. In conventional systems, gas is released throughnozzles or holes that are typically located on a central tube or on aplate in the vessel.

However, there are disadvantages associated with such conventionalsystems and methods for performing CVD. For example, using conventionalCVD processes, the temperature and pressure gradients may vary atdifferent locations within the process vessel, causing the rate andamount of deposition of the vapor material to vary from substrate tosubstrate, dependent upon the location of the substrate within theprocess vessel. In some conventional systems, vapor material release ispoorly controlled and may not be uniformly applied to the substrate. Forexample, exit apertures may become clogged. Although in some instances,a clogged tube may be re-machined to unclog the holes, in many cases,replacement of the tube is necessary, limiting the useful life of thetube. Accordingly, there is a need for gas injection systems thatprovide better control and distribution of vapor material in CVDprocesses and for gas injection systems that may be reused more readily.

SUMMARY OF THE INVENTION

A gas injector system improves distribution and directional control ofthe vapor material in a CVD or CVI process. Gas injector systems inaccordance with various embodiments may be used without experiencingsignificant clogging of gas injector tube apertures over multiple CVDprocedures. Further, various embodiments include a dual aperture releasesystem and/or allow vapor material to flow both substantiallyhorizontally and substantially vertically.

For example, various embodiments include a system comprising a gasinjector tube having at least one tube aperture disposed therethrough, ashield collar having at least one collar aperture at least partiallycorresponding to the tube aperture, wherein the shield collar isconfigured such that the tube aperture at least partially aligns withthe collar aperture,

A method comprises forming a gas injector tube having at least one tubeaperture disposed therethrough, forming a shield collar having at leastone collar aperture at least partially corresponding to the tubeaperture, wherein the shield collar is configured such that the tubeaperture at least partially aligns with the tube aperture, and couplingthe shield collar with the gas injector tube.

Further, a system comprises a first gas injector tube having a firstexterior surface, a second gas injector tube having a second exteriorsurface, a shield collar having a plurality of collar apertures, whereinthe first gas injector tube and the second gas injector tube areconfigured to be substantially coaxially aligned at a tube joint,wherein the shield collar is configured to cover a portion of the firstexterior surface and a portion of the second exterior surface, andwherein the tube joint comprises a gap between the first gas injectortube and the second gas injector tube.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B illustrate a shield collar in accordance with anembodiment;

FIG. 2 illustrates a gas injector tube with a plurality of tubeapertures in accordance with an embodiment;

FIG. 3A illustrates a gas injector tube with separate shield collars inaccordance with an embodiment;

FIG. 3B illustrates a gas injector tube coupled to shield collars inaccordance with an embodiment;

FIG. 4 illustrates a gas injector tube with a separate flanged sleeve inaccordance with an embodiment;

FIG. 5 illustrates a gas injector tube in accordance with an embodiment;

FIG. 6A illustrates a gas injector tube coupled with an end flange inaccordance with an embodiment;

FIG. 6B illustrates a gas injector tube coupled with a flanged sleeve inaccordance with an embodiment;

FIGS. 7A,7B, and 7C illustrate gas injector tubes and shield collars inaccordance with an embodiment;

FIGS. 8A and 8B illustrate the interior of a vessel comprising variousannular substrates in accordance with various embodiments;

FIG. 9 illustrates a plate in accordance with an embodiment;

FIG. 10 illustrates plate with a different aperture configuration inaccordance with an embodiment; and

FIGS. 11A and 11B illustrate a gas injector chamber in accordance withan embodiment.

DETAILED DESCRIPTION

The detailed description of exemplary embodiments herein makes referenceto the accompanying drawings, which show exemplary embodiments by way ofillustration and its best mode, and not of limitation. While theseexemplary embodiments are described in sufficient detail to enable thoseskilled in the art to practice the invention, it should be understoodthat other embodiments may be realized and that logical, chemical andmechanical changes may be made without departing from the spirit andscope of the invention. For example, the steps recited in any of themethod or process descriptions may be executed in any order and are notnecessarily limited to the order presented. Moreover, many of thefunctions or steps may be outsourced to or performed by one or morethird parties. Furthermore, any reference to singular includes pluralembodiments, and any reference to more than one component or step mayinclude a singular embodiment or step. Also, any reference to attached,fixed, connected or the like may include permanent, removable,temporary, partial, full and/or any other possible attachment option.Additionally, any reference to without contact (or similar phrases) mayalso include reduced contact or minimal contact.

In various embodiments, the injection of gas into a vessel in a CVDprocess (also referred to herein as chemical vapor or vapor material) isaccomplished without significant clogging of the gas injector tubeapertures over one or more CVD procedures. Clogging may be inhibited byusing a multiple aperture release system, wherein gas is injectedthrough successive apertures of varying sizes. For example, a dualaperture release system may comprise a more readily reusable componenthaving a plurality of apertures and a potentially less reusablecomponent having a plurality of apertures. The reusable component mayhave apertures that are larger than the apertures of the less reusablecomponent. Where there are a plurality of apertures disposed on both thereusable component and the less reusable component, the total surfacearea of the reusable component's apertures may be less than the totalsurface area of the less reusable component's apertures. The readilyreusable component's larger apertures may inhibit clogging of thecomponent, thereby enhancing the components useful life. The lessreusable component's smaller apertures may allow for directional andpressure control of the gas. As the less reusable component may besmaller and more inexpensively fabricated than the reusable component,the cost of multiple CVD/CVI processes is diminished. In variousembodiments, a readily reusable component is a gas injector tube. Invarious embodiments, the less reusable component is a shield collar.

In various embodiments, the injection of gas into a vessel in a CVDprocess is generally directionally controlled. Directional controlcomprises the distribution of gas in both a substantially horizontal andsubstantially vertical direction. Directional control may also comprisethe distribution of gas in one or more directions other than horizontalor vertical. A multidirectional flow component may comprise aperturesdisposed such that a fluid flowing through the apertures may bedirectionally controlled. For example, a shield collar may be amultidirectional flow component.

CVD may be used to deposit material onto a variety of substrates,including semiconductors and composite materials. For example, CVD maybe used with carbon fiber composite materials. CVD may be performed attemperatures from about 500° F. to about 4000° F. CVD may be performedat pressures from about 0 kPa to about 100 kPa. The injection of gasinto a vessel in a CVD process may be accomplished using one or moremethods. For example, a tube may be used to conduct gas into a furnaceor other vessel. Any suitable furnace or other vessel may be used.Further, any arrangement of the tube (or tubes) within the vessel iscontemplated. When CVD is used with substrates comprising annular orcircular disks, a tube may be disposed substantially coaxial to theannular disks. In various embodiments, a stack of substrates may begrouped together in several groups and arranged in the vessel such thateach group is at least partially separated by a plate. The plates usedmay be solid or they may have a variety of apertures that may allow gasto permeate through the plate.

Referring to FIGS. 1-11B, in various embodiments, a gas injector tubemay be used. A gas injector tube may be any tube or pipe capable ofconducting gas into a vessel. The gas injector tube may be a hollowcylindrical structure, although other geometries may also be used. A gasinjector tube may be of any length, width, or height suitable to itsparticular application. Injectors may be pipes or chambers. Chambers maybe constructed from flat plates or other geometries in variousconfigurations. The chambers may include the vessel walls as part of thechamber. For example, with reference to FIGS. 11A and 11B, one or moreflat plates may be installed against a cylindrical furnace wall forminga chamber 1101 between the at least one plate and the wall. Flat plate1101 may have aperture 1102. Generally, a tube or chamber dimension maybe scaled to vessel size and length. A tube ID or OD may range fromabout 1/64 inch to about 24 inches. A gas injector tube may beconstructed of any suitable material that is capable of withstandingtypical CVD temperatures and pressures. For example, a gas injector tubemay be constructed of steel, iron, aluminum, and/or a carbon materialsuch as graphite. In various embodiments, a gas injector tube isconstructed of graphite.

As noted above, in various embodiments, a gas injector tube 200 is ahollow cylindrical structure. In such embodiments, the walls of thecylindrical tube may be of any suitable thickness. For example, thewalls of a cylindrical gas injector tube 200 may be from about 1/64 ofan inch thick to about 6 inches thick. In various embodiments, the wallsof a cylindrical gas injector tube may be from about 4/32 of an inchthick to about ½ of an inch thick. In other applications, the walls of acylindrical gas injector tube may be 9/32 of an inch thick. At one orboth of the terminal ends of the gas injector tube, cap apertures may bemachined. As described below, cap apertures 202 suitably allow theattachment of an end cap or flanged sleeve. Cap apertures may be of anysuitable diameter. For example, cap apertures may range from about 1/64of an inch to about 24 inches.

in various embodiments, a gas injector tube has a plurality of aperturesdisposed therethrough. For example, gas injector tubes 103, 200, 500 and301 have gas injector tube apertures 105, 201, 501 and 304. Theplurality of apertures may be disposed in any pattern on the tube. Forexample, the apertures may be disposed about a common circumference ofthe gas injector tube. The apertures may also be staggered with respectto a common circumference of the gas injector tube. The apertures may beof any suitable geometry, including circular, quadrilateral, octagonal,or any other geometry. The apertures may be formed using any processsuitable for manufacturing or machining the material that comprises thegas injector tube. For example, the apertures may be formed by drilling,etching, mortising, chiseling, stamping, and/or forging. In variousembodiments, the apertures are machined into a graphite gas injectortube using a drill.

The apertures may be of any size or diameter. In various embodiments,the size of the gas tube aperture is selected so that after multipleuses, the gas injector tube aperture is less prone to clogging.Apertures may range from about 1/64 of an inch in diameter(approximately 0.39 mm) to about 2 inches (approximately 50.8 mm) indiameter. It is understood that aperture size may be expressed as thediameter of a circle but also along any side axis of the geometric shapechosen for the aperture. Apertures of about 9/32 of an inch(approximately 7.14 mm) may be used. In another application, aperturesof about ⅜ of an inch (approximately 9.52 mm) may be used. In stillother applications, apertures of about ¼ of an inch (approximately 6.35mm) may be used.

In various embodiments, a shield collar is used in conjunction with agas injector tube. A shield collar includes any structure that may becoupled to a gas injector tube. As used herein, “coupling” means theshield collar fits around or over a gas injector tube. A shield collarmay take the form of a hollow cylindrical structure and/or may furthercomprise a hollow cylindrical structure having concentric hollowcylinders. Concentric hollow cylinders may be formed where a singlehollow cylindrical structure is comprised of one or more sub-cylindershaving a different radius.

A shield collar may be constructed of any material that is also suitablefor use in a gas injector tube. With references to FIGS. 1A, 1B, 3A, and3B, shield collar 100 and 300 is a hollow cylindrical structure andcomprises concentric hollow cylinders. In such embodiments, the walls ofthe cylindrical tube may be of any suitable thickness. For example, thewalls of a cylindrical shield collar 300 may be from about 1/64 of aninch thick to about 6 inches thick. In the embodiment of FIGS. 1A and1B, the walls of a cylindrical shield collar are about ⅛ of an inch. Invarious embodiments, the walls of a cylindrical shield collar are about¼ of an inch thick.

In various embodiments, the shield collar includes a plurality ofapertures disposed therethrough. The plurality of apertures may bedisposed in any pattern on the shield collar. For example, the aperturesmay be disposed about a common circumference of the shield collar. Theapertures may also be staggered with respect to a common circumferenceof the shield collar. The shield collar apertures may be disposedperpendicular to the thickness of the shield collar, similar to theapertures disposed on the gas injector tube. There may be a gap betweena gas injector tube and a shield collar. With reference to FIGS. 1A, 1B,2, 3A, and 3B, the gap 102 between the shield collar 100 and theinjector tube 103 may direct fluid in a direction substantiallyperpendicular to aperture 101 of FIG. 1B. Similar to the gas injectortube apertures, the shield collar gap geometry may match the injectortube geometry or may be circular, quadrilateral, octagonal, or any othergeometry, and may be “off center” relative to the axis of the injectortube. The axis of a shield collar aperture and the axis of acorresponding gas injector tube aperture may at least partially overlap.Gap size may be constant or may vary along the outer surface of theinjector tube. In various embodiments, for example as illustrated inFIG. 1B, gap 102 is circular and constant around the circumference.

The shield collar gap may be formed using any process suitable forworking with the material that comprises the shield collar.

The shield collar apertures may be of any size or diameter. Aperturesmay range from about 1/64 of an inch in diameter (approximately 0.39min) to about 2 inches (approximately 50.8 mm) in diameter. It isunderstood that aperture size may be expressed as the diameter of acircle but also along any side axis of the geometric shape chosen forthe aperture. In various embodiments, shield collar apertures of about9/32 of an inch (approximately 7.14 mm) may be used. In anotherapplication, shield collar apertures of about ⅜ of an inch(approximately 9.52 mm) may be used. In still other applications, shieldcollar apertures of about ¼ of an inch (approximately 6.35 mm) may beused. For example, apertures 101 are arranged about a commoncircumference of shield collar 100. Aperture 101 is disposed such thatflow through the aperture would be directed radially from the axis ofthe shield collar. Also for example, the flow through gap 102 isdirected substantially perpendicular to the flow direction of aperture101. The gap 102 may range from about 1/64 of an inch in diameter(approximately 0.39 mm) to about 2 inches (approximately 50.8 mm). Invarious embodiments, a gap of 5/32 inch (approximately 4.0 mm) may beused.

In various embodiments, the shield collar may be coupled to a gasinjector tube. The shield collar may couple with (attach to) the gasinjector tube by fitting at least partially around or over the gasinjector tube. For example, the shield collar may be disposedsubstantially coaxial to the gas injector tube. In various embodiments,where the gas injector tube and shield collar are cylindrical, asubstantially coaxial disposition is used.

The shield collar may be fabricated to fit securely around or over thegas injector tube such that friction or a “press fit” holds the shieldcollar to the gas injector tube. Bonding materials, such as glue, epoxy,or various carbon materials may be used to affix the shield collar tothe gas injector tube. The shield collar may be fabricated to fitsecurely around or over the gas tube by bolts or pins. In variousembodiments, a shield collar may be coupled to a gas injector tube usinga securing pin though the diameter of the shield collar and the gasinjector tube. In various embodiments, securing holes are machined in agas injector tube and shield collar to accommodate a securing pin. Inother embodiments, a securing pin 302 may be inserted through a shieldcollar aperture and a gas injector tube aperture 303. For example, asecuring pin may be inserted through shield collar aperture 104 and agas injector tube aperture.

In various embodiments, the shield collar may be coupled with the gasinjector tube such that a portion of the height of the shield collar isat least partially disposed over or around the plurality of gas injectortube apertures. For example, shield collar 300 may be disposedsubstantially coaxial to gas injector tube 301. FIG. 3B shows shieldcollar 300 having a portion of its height disposed over or around theplurality of gas injector tube apertures 304.

In various embodiments, a gap exists between a shield collar and a gasinjector tube. As described here, a gap may direct fluid flow in adirection substantially perpendicular to the direction of fluid flowfrom a shield collar aperture. With reference to FIG. 1B, for example,gap 102 is shown between a gas injector tube and a shield collar.

In various embodiments, at least one of the plurality of shield collarapertures is smaller than at least one of the plurality of gas injectortube apertures. In some embodiments, the larger gas injector tubeaperture is at least partially aligned with the smaller shield collaraperture. An at least partial alignment means that when fluid flowsthrough the larger gas injector tube aperture, a portion of the fluidwould also flow through an adjacent shield collar aperture and theshield collar gap. Accordingly, in such configurations, gas may flowthrough both of the at least partially aligned apertures.

Upon exit of the gas injector tube and entry into the shield collaraperture, there may be a pressure change due to the change in aperturesize. In addition, the total surface area of the shield collar aperturesmay be larger than the total surface area of the gas injector tubeapertures. The larger surface area of the gas injector tube aperturesmeans the total flow through each shield collar is determined by the gasinjector tube apertures. The larger size gas injector tube aperture mayclog less frequently after multiple uses, and the variation of total gasflow through each shield collar over multiple uses may also be less thanin conventional systems. The size of the shield collar aperture and thegap may be selected to achieve optimum flow characteristics based uponthe particular substrate, the gas used, the amount of gas, and/or theamount of flow through the gap to be directed substantiallyperpendicular to the flow direction of the apertures.

In various embodiments, the alignment of the apertures is such that theapertures are coaxial to each other or substantially coaxial to eachother, although any amount of overlap of the apertures such that wouldallow gas flow through both apertures is contemplated. As used herein, acollar aperture corresponds to a tube aperture when the collar apertureis located to at least partially overlap the corresponding tube aperturewhen the gas injector tube and the shield collar are coupled. Forexample, shield collar 300 may couple with gas injector tube 301 suchthat shield collar apertures 305 substantially align with gas injectortube apertures 304. In this manner, gas may flow through the larger tubeapertures and the smaller shield collar apertures and shield collar gap.

As noted above, an end cap or flanged sleeve may be used at one or bothterminals of a gas injector tube. For an embodiment, an end cap includesany component that seals one terminus of a gas injector tube. A flangedsleeve includes any component used for input of gas and/or forattachment to hold or orient the gas injector tube. An end cap orflanged sleeve may be constructed of any material suitable forconstructing a gas injector tube. For example, in various embodiments,an end cap and flanged sleeve are made of graphite.

An end cap may have an interior portion that extends into the terminusof a gas injector tube. In embodiments where cylindrical gas injectortubes are used, the end cap may include an interior portion that is thesame diameter as the inside diameter of the gas injector tube. End cap306 is shown in FIG. 3A. An end cap's interior portion may furthercomprise pin apertures 307.

An end cap or flanged sleeve may also include a flange portion. Inembodiments where cylindrical gas injector tubes are used, the end cap'sflange portion or a flanged sleeve may be of the same or greaterdiameter as the outside diameter of the gas injector tube. In suchembodiments, a flanged sleeve may accept a terminus of a gas injectortube within the inside of the sleeve. Flanged sleeve 400 is shown inFIG. 4 having a sleeve portion 401, flange portion 402, and pin aperture405. Carbon foil may be used at an end cap and gas injector tube jointor between a flanged sleeve and other components. For example, carbonfoil may be placed at an interface between the flange portion 402 of theflanged sleeve 400 and a plate 900 and 1000 shown in FIG. 9 and FIG. 10.Also for example, carbon foil may be placed at interface 602 between theflanged sleeve and an end flange 600. An end flange may have an aperture601. As shown in FIG. 6A, the aperture 601 may be any size equal orsmaller than the inside of flanged sleeve 400. The total gas flow to gasinjector tube 406 may be determined by aperture 601.

An end cap or flanged sleeve may be secured to a gas injector tube. Anysuitable method of securing an end cap or flanged sleeve to the gasinjector tube may be used. For example, bonding materials, such as glue,epoxy, or various carbon materials may be used to couple the end cap orflanged sleeve to the gas injector tube. In various embodiments, one ormore pins may be used to couple an end cap or flanged sleeve to the gasinjector tube. Such pins may be constructed of any material suitable forconstructing a gas injector tube. In various embodiments, pins are madeof graphite. Pins may be inserted through the end cap apertures on a gasinjector tube and the pin apertures on an end cap. Pins may also beinserted through the flanged sleeve apertures 203 on a gas injector tubeand the pin apertures on a flanged sleeve. For example, pin 403 may passthrough gas injector tube aperture 404 and flanged sleeve aperture 405.With reference to FIGS. 6A and 6B, flanged sleeve apertures 404 and 405are shown.

In various embodiments, one or more gas injector tubes are coupled intoa single assembly. For example, two gas injector tubes may be alignedcoaxially or partially overlapping. One terminus of each gas injectortube may be coupled to a shield collar. When coupled, a gap between eachinjector tube may be provided to allow gas to flow through the shieldcollar. For example, with reference to FIG. 7A, 7B, and 7C, gas injectortubes 700 and 701 may be disposed substantially coaxial and coupledusing shield collar 703. When coupled, the terminuses of gas injectortubes 700 and 701 form a gap within the shield collar, allowing gas toflow through the gap and through the shield collar apertures 702 and704. Shield collar 703 may be used in such embodiments. Shield collar703 has collar aperture 702 and collar aperture 704 which are positionedsubstantially perpendicular relative to each other. Shield collar 703also includes step down 705. To couple, a terminus of gas injector tube700 may be positioned on or within step down 705. FIG. 8A illustrates anembodiment having one or more gas injector tubes coupled into a singleassembly 700 and their relation to an exemplary substrate. FIG. 8Billustrates an embodiment using injector 500 in relation to an exemplarysubstrate. Seal 806 may be disposed on top of a stack of substrates 804and 807. Seal 806 may also be disposed on top of plates 805. Seal 806may be made of any suitable material, including carbon foil and/orgraphite. Plate 805 separates stack 804 and stack 807. Gas injector tubeapertures 501 allow for fluid flow. The seals 806 three gas to flowsubstantially between individual substrates in 804 or in 807.

Chemical vapor material used in conjunction with various embodiments maybe any gas having one or more components capable of decomposing to forma solid residue on or within a substrate. In various embodiments, gascomprises one or more reactant components and/or one or more carriercomponents.

The reactant component of a gas may be capable of forming a residue uponthermal decomposition. For example, when carbon is the desired residue(as in the formation of carbon/carbon composites), the reactantcomponent may comprise one or more hydrocarbons. Suitable hydrocarbonsinclude alkanes such as straight chain, branched chain and/or cyclicalkanes. The alkane may have, for example, from about 1 to about 8carbon atoms, and more specifically, from about 1 to about 6 carbonatoms, and more specifically, from about 1 to about 3 carbon atoms.Examples of alkanes include methane, ethane, propane, cyclopentane, ormixtures thereof In other embodiments, the reactant component maycomprise one or more alkenes, having for example, about 2 to about 8carbon atoms, alone or in addition to one or more alkanes. Further,borontrichloride and/or chlorosilanes such as methyltrichlorosilane ordimethyldicholorosilane may be used. Still further, silicon by usingsilane, silicon nitride by using silane and ammonia, or SiO2 may bedeposited using oxygen, dichlorosilane, nitrous oxide, ortetraethylorthosilicate. Many metals may be deposited by CVI) usingchlorides, florides, or at low temperature by carbonyl precursors. Thesemetals include but are not limited to rhenium, tungsten, molybdenum,tantalum, and nickel. Many organometallic compounds are in use fordeposited metals, semiconductors, and ceramics. For example, GaAs CVDcan be done with Arsine and trimethylgallium.

The carrier component includes a gas suitable to carry and/or dilute thereactant component. The carrier component may comprise hydrogen,nitrogen, helium, argon, or a mixture of two or more thereof It will beunderstood that the carrier component may comprise any diluent and/orinert gases.

As used herein, a “substrate” includes materials capable of beingtreated by CVD/CVI. In various embodiments, a substrate comprises aporous material having sufficient pore size and volume to permit a gasto infiltrate the pores under reaction conditions to form a solidresidue therein as a result of thermal decomposition. Examples ofsuitably porous materials include, for example, carbon, silicon, boron,silicon carbide, silicon nitride, aluminum nitride, titanium nitride,boron carbide, cubic zirconia and the like, or a mixture of two or morethereof.

In accordance with various embodiments, the porous material is formedfrom a fibrous material, such as carbon fibers and the like. The carbonfibers may be derived from polyacrylonitrile, rayon (synthetic fiberderived from cellulose), pitch and the like. In an embodiment, theporous substrate is formed by twisting together or otherwise joining thefibers to form a fiber yarn. The yarn may be woven, braided, knitted orotherwise joined into layers of fibrous material. These layers are thencombined to form a porous substrate.

In various embodiments, the substrate comprises a substantially solidmaterial. For example, composite materials may be used as substrates inCVD. However, it will be understood that a substrate may comprise anymaterial (whether porous or solid) that is capable of being treated byCVI and/or CVD.

The substrate may comprise any desired shape or form. For example, thesubstrate may be in the form of a polygon, such as a triangle, a square,rectangle, pentagon, hexagon, octagon, and the like. Similarly, thesubstrate may be other shapes, including symmetrical and asymmetricalshapes. In various embodiments, the substrate may be in the form acircular or annular disk.

In various embodiments, a stack of substrates are grouped together inseveral groups and arranged in the vessel such that each group isseparated by a plate. The plates used may be solid or they may have avariety of apertures that may allow gas to permeate through the plate.The substrates may be separated, for example using spacers, or they maybe stacked surface to surface. In some embodiments, substrates arestacked surface to surface, meaning that substrates are stacked incouples such that one surface of each substrate is in contact with eachother. In such a configuration, only one surface of each substrate willhave the vapor material deposited onto it.

For example, with reference to FIG. 8A, 8B, vessel 803 contains twostacks of substrates 800, 801, 804 and 807. The stacks 800 and 801 areseparated by plate 802. Plate 802 may be constructed of any materialcapable of withstanding CVD/CVI operating temperatures and pressures.Plate 802 may lack apertures or may have apertures disposed in anypattern, such as depicted in plate 900 and plate 1000. Gas injector tube700 is coupled to shield collar 703. Shield collar 703 may haveapertures 702 and 704 to allow gas to flow both horizontally andvertically through and over the stack Gas injector tube 700 can be of atype shown in FIG. 3. Gas injector tube 301 is coupled to shield collar300. The apertures 305 and gap 102 allow gas to flow both horizontallyand vertically through and over the stack. In such a configuration,substrate coating may be directionally controlled, allowing for improveddeposition of material. Moreover, the use of shield collars may extendthe useful life of the gas injector tube,

With reference to FIGS. 8B and 5, gas injector tube 500 may haveapertures 501 aligned with the inside of stacks of substrates. Twostacks of substrates 804 and 807 are shown. The stacks 804 and 807 areseparated by plate 805. Plate 805 may be constructed of any materialcapable of withstanding CVD/CVI operating temperatures and pressures.Plate 805 may lack apertures or may have apertures disposed in anypattern, such as depicted in plate 900 and plate 1000. The top andbottom of the stacks of substrates may be partially or completely sealedwith an appropriate sealing component comprised of other materialcapable of withstanding CVD/CVI operating temperatures and pressures.Sealing components may be made of various carbon based materials and mayassume various geometries. For example, sealing component 806 is a diskmade of graphite. Seal 806 is disposed on top of a stack of substrates804 and 807. In addition, seal 806 is placed on plates 805 below thestack of substrates 804 and 807. The gas flow may be focused out fromthe center and between the substrates separated by spacers.

Benefits, other advantages, and solutions to problems have beendescribed herein with regard to specific embodiments. However,thebenefits, advantages, solutions to problems, and any elements that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as critical, required, or essentialfeatures or elements of the invention. The scope of the invention isaccordingly to be limited by nothing other than the appended claims, inwhich reference to an element in the singular is not intended to mean“one and only one” unless explicitly so stated, but rather “one ormore.” Moreover, where a phrase similar to “at least one of A, B, or C”is used in the claims, it is intended that the phrase be interpreted tomean that A alone may be present in an embodiment, B alone may bepresent in an embodiment, C alone may be present in an embodiment, orthat any combination of the elements A, B and C may be present in asingle embodiment; for example, A and B, A and C, B and C, or A and Band C. Furthermore, no element, component, or method step in the presentdisclosure is intended to be dedicated to the public regardless ofwhether the element, component, or method step is explicitly recited inthe claims. No claim element herein is to be construed under theprovisions of 35 U.S.C. 112, sixth paragraph, unless the element isexpressly recited using the phrase “means for.” As used herein, theterms “comprises”, “comprising”, or any other variation thereof, areintended to cover a non-exclusive inclusion, such that a process,method, article, or apparatus that comprises a list of elements does notinclude only those elements but may include other elements not expresslylisted or inherent to such process, method, article, or apparatus.

1. A system comprising: a gas injector tube having a radially disposed tube aperture through a wall of said gas injector tube; and a shield collar having a collar aperture at least partially radially corresponding to said tube aperture, said shield collar configured so that said collar aperture at least partially aligns with said tube aperture.
 2. The system of claim 1, wherein said tube aperture is larger than said collar aperture.
 3. The system of claim 1, wherein said shield collar has a plurality of collar apertures.
 4. The system of claim 2, wherein said plurality of collar apertures is configured to direct gas flow horizontally and vertically.
 5. The system of claim 3, wherein said gas injector tube has a plurality of tube apertures and wherein said tube apertures are covered by said shield collar.
 6. The system of claim 3, wherein said gas injector tube has a plurality of tube apertures and wherein the total surface area of said tube apertures is smaller than the total surface area of said collar apertures.
 7. The system of claim 1, wherein said shield collar is configured to be coaxially aligned with said gas injector tube.
 8. The system of claim 1, wherein said gas injector tube and said shield collar are comprised of a carbon material.
 9. The system of claim 1, wherein said gas injector tube and said shield collar are comprised of graphite.
 10. The system of claim 1, further comprising an end cap configured to be coupled to a terminus of said gas injector tube.
 11. The system of claim 1, further comprising a flanged sleeve configured to be coupled to a terminus of said gas injector tube.
 12. The system of claim 11, wherein said end cap is configured to be coupled to a terminus of said gas injector tube via a graphite pin.
 13. A system comprising a first gas injector tube having a first exterior surface; a second gas injector tube having a second exterior surface; a shield collar having a plurality of radially disposed collar apertures; wherein said first gas injector tube and said second gas injector tube are configured to at least partially overlap at a tube joint; wherein said shield collar is configured to coaxially align with said first gas injector tube and said second gas injector tube to cover a portion of said first exterior surface and a portion of said second exterior surface; and wherein said tube joint comprises a gap between said first gas injector tube and said second gas injector tube.
 14. The system of claim 13, wherein said plurality of collar apertures is configured to direct gas flow horizontally and vertically.
 15. The system of claim 13, wherein said first gas injector tube comprises a plurality of tube apertures.
 16. The system of claim 13, wherein said first gas injector tube and said shield collar are comprised of a carbon material.
 17. The system of claim 13, wherein said first gas injector tube and said shield collar are comprised of graphite.
 18. The system of claim 13, further comprising an end cap configured to be coupled to a terminus of said first gas injector tube.
 19. The system of claim 18, wherein said end cap is configured to be coupled to a terminus of said first gas injector tube via a graphite pin. 